Preparation of vinyl ester amides of pinic acid and copolymers thereof with vinyl chloride



United States Patent 3,544,529 PREPARATION OF VINYL ESTER AMIDES OFPINIC ACID AND COPOLYMERS THEREOF WITH VINYL CHLORIDE Glen W. Hedrick,Lake City, Fla., and Frank C. Magne, New Orleans, La., assignors to theUnited States of America as represented by the Secretary of AgricultureNo Drawing. Filed June 20, 1967, Ser. No. 647,343

Int. Cl. C08f 15/34, 15/08 U.S. Cl. 260-785 4 Claims ABSTRACT OF THEDISCLOSURE A non-exclusive, irrevocable, royalty-free license in theinvention herein described, throughout the world for all purposes of theUnited States Government, with the power to grant sublicenses for euchpurposes, is hereby granted to the Government of the United States ofAmerica.

A primary object of the present invention is to provide methods forpreparing at will some vinyl ester amides of pinic acid. A furtherobject of this invention is to provide methods for preparing vinylchloride copolymers from these ester amides.

Polyvinyl chloride is plasticized by pinic diesters (Loeblich, V. M.,Magne, F. C., and Mod, R. R., Ind. Eng. Chem., 47, 855 (1955) and Coyne,R. F., and Yehle, E. A., Ind. Eng. Chem., 47, 853 (1955 but copolymersof vinyl chloride with various isomeric pinic acid esters (I and II),

R'o2o- -omo 02m R2020 01120 02R CH3\CH3 on. on

(where R:CH=CH and R =C H n-C H or CH CI-I(CH CH did not exhibitinternal plasticization by the vinyl ester incorporated in the polymerbackbone (Marvel, C. S., Shimura, Y., and Magne, F. C., J. Polymer Sci,45, 13 (1960)).

Since amides are often good plasticizers of polyvinyl chloride, thevinyl ester-amides of pinic acid, HI, where the amine moiety ismorpholine (a), piperidine (b), or di-n-butylamine (c), were prepared.

Copolymers containing approximately 15 and 30 weight percent of thevinyl ester-amide were prepared to examine the ability of thesecomonomers to act as internal plasticizers for the polymers.

The vinyl esters of 2,2-dimethyl-3-alkylaminocarbonylcyclobutane aceticacid were prepared by reacting the fol- 3,544,529 Patented Dec. 1, 1970lowing amino morpholine, piperidine and di-n-butyl amine with ethyl2,2-dimethyl-3-chlorocarbonylcyclobutane acetate, by hydrolyzing theethyl ester to the free acid and vinylating the resulting monoamides byvinyl interchange. Results are shown in Table I.

The vinyl chloride copolymers containing approximately 25 and 30 weightpercent of the vinyl ester-amide were prepared in an emulsion system at60 C. using ORR soap as the emulsifying agent and potassium persulfateas the initiator. The copolymers were reprecipitated 1 5 times fromtetrahydrofuran into water and 3 times into methanol before analysis.

The evaluations of the copolymers obtained on specimens die-cut from37-54 mil thick sheets prepared by casting on a confined mercurysurface, a tetrahydrofuran solution containing 15 grams of therespective copolymers, 0.075 gram of stearic acid and 0.15 gram ofAdvastab T-360 stabilizer (a polymeric tin mercaptide-Advance Division,Carlisle Chemical Works). After setting for 48 hours at room temperatureto allow the bulk of the solvent to evaporate, the sheets were strippedfrom the mercury surface and aged for 24 hours at room temperature. Theywere then heated in a forced draft oven for 12 hours at 65 C. followedby another aging at room temperature for 30 days to desolventize thefilm. The copolymers were then tested for tensile strength, modulus ofelasticity, yield point and elongation measurements were made inconformance with ASTM Test D638 for rigid and semirigid conditions,except for the use of l-inch gauge length rather than the 2 inchescalled for in the test. Torsional stiffness measurements were made inconformance to ASTM Test 1043- 61T. The results of these tests are shownin Table 1H.

EXAMPLE 1 The acid chloride, B.P. 114 C., 2 mm., of monoethyl pinate,was prepared by reacting thionyl chloride with the monoester obtained byesterification of pinic acid with one mole of ethanol- (Lewis, I. B.,and Hedrick, G. W., J. Org. Chem., 24, 1870 (1959)). The pinic acid wasobtained from hypochlorite oxidation of cis-dl-pinonic acid. Gaschromatographic analyses of esters of the pinic acid gave two peakswhich presumably resulted from the expected cis and trans isomers of theacid.

EXAMPLE 2 Morpholine, 378 g. (4.35 moles) dissolved in 1 liter of drybenzene was heated to reflux. The acid chloride above was added dropwiseat a rate to maintain a gentle boil. When cooled to room temperature,morpholine hydrochloride, insoluble in benzene, was removed byfiltration and washed with benzene. After the solvent was removed underreduced pressure, the product was distilled. The yield was 444 g. of aliquid.

EXAMPLE 3 The amide above, 283 g. (1 mole), was dissolved in 300 ml. ofethanol and saponified by the addition of 40 g. of sodium hydroxidedissolved in ml. of water. The temperature rose to 50 C. and after 4hours the pH dropped to about 8. After 16 hours the batch was dilutedwith 169 ml. of water, the alcohol removed by distillation using apacked column and the residue diluted further with 422 ml. of water.Extraction of the alkaline solution with chloroform gave 9.5 g. ofstarting material. Acidification, extraction with chloroform andisolation by removal of solvent at 0.5 mm., C. pot temperature gave 261g. of waxy solid. Five grams crude washed with diethyl ether gave 3 g.of colorless liquid, presumably the cis isomer since it was present inthe greater amount.

The crude half amide above was vinylated by the vinylinterchangeprocedure of Adelman (Adelman, R. L., J. Org. Chem., 14, 1057 (1949)).The crude amide was melted and added in a molten state to the vinylacetate. After adding catalyst and standing awhile, crystallization ofone of the half amide, presumably the cis isomer occurred. After about72 hours, the solid, about one-third of the charge, was removed byfiltration. The vinyl ester (filtrate) was isolated byrthe usualprocedure which in volved stripping excess vinyl acetate in vacuo,washing with dilute sulfuric acid, 0.1 to 0.5 N, then water, drying oversodium sulfate and distilling. The recovered acid was reacted with morevinyl acetate and converted to vinyl ester.

EXAMPLE The piperidine derivative was prepared as in Example 2 exceptpiperidine was used in place of morpholine. The ethyl ester was thenhydrolyzed to the free acid as in Example 3 and the monoamide wasvinylated by the vinyl interchange procedure as in Example 4.

EXAMPLE 6 The di-n-butyl amine derivative was prepared as in Example 2except di-n-butyl amine was used in place of morpholine. The ethyl esterwas then hydrolyzed to the free acid as in Example 3 and the monoamidevinylated by the vinyl interchange procedure as in Example 4.

EXAMPLE 7 The vinyl chloride copolymers containing 25 and 30 weightpercent of vinyl 2,2-dimethyl-3-morpholinocarbonylcyclobutane acetate,vinyl 2,2-dimethyl-3-piperidinocarbonylcyclobutane acetate and vinyl2,2-dimethyl-3-di-nbutylaminocarbonylcyclobutane acetate were preparedin the following manner:

Each evaluation sample was obtained by combining 1015'individua1polymerization batches during the reprecipitation procedure. Eachindividual polymerization contained a starting charge of 10 g. ofmonomers (2.5 g. and 7.5 g. or 3.0 g. and 7.0 g. of the vinylester-amide and vinyl chloride, respectively). To a 110 m1.polymerization tube (Ace Glass T1506) was added the approximate amountof vinyl ester-amide, 0.6 g. of ORR soap, 4.0 ml. of a 2.5% potassiumpersulfate solution and 43 ml. of deoxygenated water. The vinyl2,2-dimethyl-3-morpholinocarbonylcyclobutane acetate copolymers wereprepared using Triton X-301 (Rohm & Haas), a 20% solution of analkylaryl sulfonate and 40 ml. of water. The tube was cooled in a DryIce-acetone bath and a slight excess of condensed vinyl chloride wasadded. The tube was capped with a crown type bottle top after the excessvinyl chloride was evaporated.

The ORR soap mentioned above is a silicate free and linoleic acidlinolinic acid free soap used in the production of GRS rubber.

The polymerization tubes were placed in a constant temperature tumblerbatch for 72 hours at 60 C. The copolymer emulsions were coagulated bypouring into 400 m1. of a saturated salt solution. The copolymer batchwas filtered, washed two times with water and two times with methanol.The copolymer was dissolved in tetrahydrofuran (10% solution) andreprecipitated a total of times into water and 2 times into methanol.

A one gallon Waring Blendor was used for the reprecipitation into water.The rate of agitation was about 7000 r.p.m. The methanol was stirredwith a spatula 4 during the reprecipitations. The copolymersprecipitated in fibrous stands during the reprecipitation into water andmethanol under the conditions described.

The copolymers were dried in air for 72 hours and in a vacuum oven atroom temperature for 24 hours. The copolymer data are listed in TableII.

We claim:

1. A copolymer comprising a major portion of vinyl chloride and fromabout 25 to 30 weight percent, based on the weight of the copolymer, ofa vinyl ester-amide selected from the group consisting of o 0 CH2=CHO(JCH (ii-N 0 CHa CH:

eel/Q CH3 CHa and Q 0 4 is t CHFCHO- CH N C H n on. on. 4

copolymerized with said vinyl chloride.

2. A copolymer comprising a major portion of vinyl chloride and fromabout 25 to 30 Weight percent, based on the weight of the copolymer, ofa vinyl ester-amide of the formula copolymerized with said vinylchloride.

3. A copolymer comprising a major portion of vinyl chloride and fromabout 25 to 30 weight percent, based on the weight of the copolymer, ofa vinyl ester-amide of the formula 0 0 CHz=CHO-iCHz ii- 6 CH3 CH3coplymerized with said vinyl chloride.

References Cited Griffin et al., J. P. Sci., Pt A-l, 4(8), 1993-2002,Aug. 1966.

MURRAY TILLMAN, Primary Examiner C. J. SECCURO, Assistant Examiner U.S.Cl. X.R.

